JPWO2015137343A1 - Fluorine-containing boric acid composite particles - Google Patents
Fluorine-containing boric acid composite particles Download PDFInfo
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- JPWO2015137343A1 JPWO2015137343A1 JP2015539906A JP2015539906A JPWO2015137343A1 JP WO2015137343 A1 JPWO2015137343 A1 JP WO2015137343A1 JP 2015539906 A JP2015539906 A JP 2015539906A JP 2015539906 A JP2015539906 A JP 2015539906A JP WO2015137343 A1 JPWO2015137343 A1 JP WO2015137343A1
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- Prior art keywords
- fluorine
- boric acid
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- carbon atoms
- general formula
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 106
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000011737 fluorine Substances 0.000 title claims abstract description 104
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000004327 boric acid Substances 0.000 title claims abstract description 77
- 239000011246 composite particle Substances 0.000 title claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 49
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 31
- 125000006551 perfluoro alkylene group Chemical group 0.000 claims abstract description 18
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 11
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- -1 ether diol Chemical class 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000002296 dynamic light scattering Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 20
- VSQAMHLYSYQSBM-UHFFFAOYSA-N [F].OB(O)O Chemical compound [F].OB(O)O VSQAMHLYSYQSBM-UHFFFAOYSA-N 0.000 abstract 1
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 22
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 17
- 150000001298 alcohols Chemical class 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000011521 glass Substances 0.000 description 14
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 9
- 229940094933 n-dodecane Drugs 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000035992 intercellular communication Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical group C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000007962 solid dispersion Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- NKLYMYLJOXIVFB-UHFFFAOYSA-N triethoxymethylsilane Chemical compound CCOC([SiH3])(OCC)OCC NKLYMYLJOXIVFB-UHFFFAOYSA-N 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- TUQLLQQWSNWKCF-UHFFFAOYSA-N trimethoxymethylsilane Chemical compound COC([SiH3])(OC)OC TUQLLQQWSNWKCF-UHFFFAOYSA-N 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- PSQZJKGXDGNDFP-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)(F)F PSQZJKGXDGNDFP-UHFFFAOYSA-N 0.000 description 1
- PJRIQFXPYMVWOU-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,5-nonafluoropentan-1-ol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F PJRIQFXPYMVWOU-UHFFFAOYSA-N 0.000 description 1
- JUGSKHLZINSXPQ-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluoropentan-1-ol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)C(F)F JUGSKHLZINSXPQ-UHFFFAOYSA-N 0.000 description 1
- NBUKAOOFKZFCGD-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)F NBUKAOOFKZFCGD-UHFFFAOYSA-N 0.000 description 1
- LVFXLZRISXUAIL-UHFFFAOYSA-N 2,2,3,4,4,4-hexafluorobutan-1-ol Chemical compound OCC(F)(F)C(F)C(F)(F)F LVFXLZRISXUAIL-UHFFFAOYSA-N 0.000 description 1
- HDBGBTNNPRCVND-UHFFFAOYSA-N 3,3,3-trifluoropropan-1-ol Chemical compound OCCC(F)(F)F HDBGBTNNPRCVND-UHFFFAOYSA-N 0.000 description 1
- JPMHUDBOKDBBLG-UHFFFAOYSA-N 3,3,4,4,4-pentafluorobutan-1-ol Chemical compound OCCC(F)(F)C(F)(F)F JPMHUDBOKDBBLG-UHFFFAOYSA-N 0.000 description 1
- JCMNMOBHVPONLD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohexan-1-ol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F JCMNMOBHVPONLD-UHFFFAOYSA-N 0.000 description 1
- GRJRKPMIRMSBNK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctan-1-ol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F GRJRKPMIRMSBNK-UHFFFAOYSA-N 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
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- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C01B35/06—Boron halogen compounds
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- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
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- C03C17/328—Polyolefins
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/58—Metal-containing linkages
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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Abstract
一般式 RF-A-OH(ここで、RFは炭素数6以下のパーフルオロアルキル基であり、またはパーフルオロアルキル基のフッ素原子の一部が水素原子で置換され、炭素数6以下の末端パーフルオロアルキル基および炭素数6以下のパーフルオロアルキレン基を含んで構成されるポリフルオロアルキル基であり、Aは炭素数1〜6のアルキレン基である)で表される含フッ素アルコールとホウ酸との縮合体からなる含フッ素ホウ酸コンポジット粒子が提供される。含フッ素ホウ酸コンポジット粒子は、含フッ素アルコールと含フッ素アルコールに対してモル比1.0以下のアルコキシシランとの両者およびホウ酸の縮合体であってもよい。これらの含フッ素コンポジット粒子は、無機質基材等に対して良好な密着性を有する。General formula RF-A-OH (wherein RF is a perfluoroalkyl group having 6 or less carbon atoms, or a part of fluorine atoms of the perfluoroalkyl group is substituted with a hydrogen atom, and a terminal perfluoroalkyl group having 6 or less carbon atoms is substituted. A fluorine-containing alcohol represented by a fluoroalkyl group and a perfluoroalkylene group having 6 or less carbon atoms, and A is an alkylene group having 1 to 6 carbon atoms) and boric acid Fluorine-containing boric acid composite particles comprising the condensate of are provided. The fluorine-containing boric acid composite particles may be a condensate of both a fluorine-containing alcohol and an alkoxysilane having a molar ratio of 1.0 or less with respect to the fluorine-containing alcohol and boric acid. These fluorine-containing composite particles have good adhesion to inorganic substrates and the like.
Description
本発明は、含フッ素ホウ酸コンポジット粒子に関する。さらに詳しくは、表面処理特性を改善せしめた含フッ素ホウ酸コンポジット粒子に関する。 The present invention relates to fluorine-containing boric acid composite particles. More specifically, the present invention relates to fluorine-containing boric acid composite particles having improved surface treatment characteristics.
無機材料表面を各種の化合物やポリマーでコーティングすることにより、様々な表面特性を発現させることが知られている。中でも、フッ素系化合物を表面処理に使用した場合には、フッ素原子の有する特性から、撥水性だけではなく撥油性の点でも表面改質できるので、様々な基材へのコーティングに利用されている。 It is known that various surface characteristics are expressed by coating the surface of an inorganic material with various compounds and polymers. In particular, when fluorine-based compounds are used for surface treatment, the surface properties can be modified not only for water repellency but also for oil repellency because of the properties of fluorine atoms, so they are used for coating on various substrates. .
特に、C8のパーフルオロアルキル基を有する表面処理剤を基質に塗布するとことで、高い撥水撥油性を示すコーティングが可能であるが、近年C7以上のパーフルオロアルキル基を有する化合物が、細胞株を用いた試験管内試験において、発がん因子と考えられている細胞間コミュニケーション阻害をひき起すこと、かつこの阻害は官能基ではなく、フッ素化された炭素鎖長に依存し、炭素鎖が長いもの程阻害力が高いことが報告されており、フッ素化された炭素数の長い化合物を使用したモノマーの製造が制限されるようになってきている。In particular, by applying a surface treatment agent having a C 8 perfluoroalkyl group to a substrate, a coating showing high water and oil repellency is possible, but in recent years, a compound having a C 7 or more perfluoroalkyl group has In vitro tests using cell lines cause intercellular communication inhibition, which is considered to be a carcinogenic factor, and this inhibition is not a functional group but depends on the fluorinated carbon chain length, and the carbon chain is long It has been reported that the higher the inhibition power, the more limited the production of monomers using fluorinated compounds with a long carbon number.
また、炭素数が6以下のパーフルオロアルキル基を有する含フッ素アルコールにあっては、ガラス、金属、石材等の無機質基材への密着性に欠けるという問題もみられる。 In addition, the fluorine-containing alcohol having a perfluoroalkyl group having 6 or less carbon atoms has a problem that it lacks adhesion to an inorganic base material such as glass, metal, and stone.
特許文献1〜2には、含フッ素アルコール、アルコキシシラン(および重合性官能基含有アルコール)を縮合反応させることが記載されているが、得られたアルコキシシラン誘導体は、光酸発生剤または光塩基発生剤を添加した硬化性組成物、あるいは無機導電塗料組成物の調製に用いられている。 Patent Documents 1 and 2 describe that a fluorine-containing alcohol and an alkoxysilane (and a polymerizable functional group-containing alcohol) are subjected to a condensation reaction. The obtained alkoxysilane derivative is a photoacid generator or a photobase. It is used for the preparation of a curable composition to which a generator is added, or an inorganic conductive coating composition.
本発明の目的は、環境中に放出されてもパーフルオロオクタン酸等を生成させず、しかも短鎖の化合物に分解され易いユニットを有する含フッ素アルコールを用い、無機質基材等に対する密着性を有する含フッ素ホウ酸コンポジット粒子を提供することにある。 An object of the present invention is to use a fluorinated alcohol having a unit that does not generate perfluorooctanoic acid or the like even when released into the environment and is easily decomposed into a short-chain compound, and has adhesion to an inorganic substrate or the like. The object is to provide fluorine-containing boric acid composite particles.
本発明によって、一般式
RF-A-OH 〔I〕
(ここで、RFは炭素数6以下のパーフルオロアルキル基であり、またはパーフルオロアルキル基のフッ素原子の一部が水素原子で置換され、炭素数6以下の末端パーフルオロアルキル基および炭素数6以下のパーフルオロアルキレン基を含んで構成されるポリフルオロアルキル基であり、Aは炭素数1〜6のアルキレン基である)で表される含フッ素アルコールとホウ酸との縮合体からなる含フッ素ホウ酸コンポジット粒子が提供される。含フッ素ホウ酸コンポジット粒子は、含フッ素アルコール〔I〕と含フッ素アルコールに対してモル比1.0以下のアルコキシシランとの両者およびホウ酸の縮合体であってもよい。According to the invention, the general formula
R F -A-OH (I)
(Wherein R F is a perfluoroalkyl group having 6 or less carbon atoms, or a part of the fluorine atom of the perfluoroalkyl group is substituted with a hydrogen atom, and the terminal perfluoroalkyl group having 6 or less carbon atoms and the carbon number A polyfluoroalkyl group composed of 6 or less perfluoroalkylene groups, and A is an alkylene group having 1 to 6 carbon atoms). Fluoroboric acid composite particles are provided. The fluorine-containing boric acid composite particles may be a condensate of both a fluorine-containing alcohol [I] and an alkoxysilane having a molar ratio of 1.0 or less with respect to the fluorine-containing alcohol and boric acid.
また、本発明によって、一般式
RF′-A-OH 〔Ia〕
または一般式
HO-A-RF′′-A-OH 〔Ib〕
(ここで、RF′は炭素数6以下の末端パーフルオロアルキル基および炭素数6以下のパーフルオロアルキレン基を有する、O、SまたはN原子を含有する直鎖状または分岐状パーフルオロアルキル基であり、RF′′は炭素数6以下のパーフルオロアルキレン基を有する、O、SまたはN原子を含有する直鎖状または分岐状のパーフルオロアルキレン基であり、Aは炭素数1〜6のアルキレン基である)で表される含フッ素アルコールとホウ酸との縮合体からなる含フッ素ホウ酸コンポジット粒子が提供される。含フッ素ホウ酸コンポジット粒子は、含フッ素アルコール〔Ia〕または〔Ib〕とこれら含フッ素アルコールに対してモル比1.0以下のアルコキシシランとの両者およびホウ酸の縮合体であってもよい。Also, according to the invention, the general formula
R F ′ -A-OH (Ia)
Or general formula
HO-AR F ′ ′ -A-OH (Ib)
(Wherein R F ′ is a linear or branched perfluoroalkyl group containing an O, S or N atom having a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms. R F ″ is a linear or branched perfluoroalkylene group containing an O, S or N atom having a perfluoroalkylene group having 6 or less carbon atoms, and A is 1 to 6 carbon atoms. Fluorine-containing boric acid composite particles comprising a condensate of a fluorine-containing alcohol and boric acid represented by formula (1) are provided. The fluorine-containing boric acid composite particles may be a condensate of both fluorine-containing alcohol [Ia] or [Ib] and an alkoxysilane having a molar ratio of 1.0 or less with respect to these fluorine-containing alcohols and boric acid.
本発明で用いられる含フッ素アルコールは、末端パーフルオロアルキル基やポリフルオロアルキル基中のパーフルオロアルキレン鎖の炭素数が6以下のものであり、短鎖の含フッ素化合物に分解され易いユニットを有しているため、環境汚染につながらない。また、得られた含フッ素ホウ酸コンポジット粒子は、基材表面に良好な撥水撥油性、防汚機能性を示す薄膜を形成させ、この薄膜は無機質基材等に対する密着性にもすぐれている。 The fluorine-containing alcohol used in the present invention has a perfluoroalkylene chain having 6 or less carbon atoms in the terminal perfluoroalkyl group or polyfluoroalkyl group, and has a unit that is easily decomposed into a short-chain fluorine-containing compound. Therefore, it does not lead to environmental pollution. In addition, the obtained fluorinated boric acid composite particles form a thin film having good water / oil repellency and antifouling function on the surface of the substrate, and this thin film has excellent adhesion to an inorganic substrate or the like. .
含フッ素アルコール〔I〕としては、例えば一般式
CnF2n+1(CH2)jOH 〔II〕
n:1〜6、好ましくは4〜6
j:1〜6、好ましくは1〜3、特に好ましくは2
で表されるポリフルオロアルキルアルコール等が用いられる。As the fluorine-containing alcohol [I], for example, a general formula
C n F 2n + 1 (CH 2 ) j OH (II)
n: 1-6, preferably 4-6
j: 1 to 6, preferably 1 to 3, particularly preferably 2
The polyfluoroalkyl alcohol represented by these is used.
アルキレン基Aとしては、-CH2-基、-CH2CH2-基等が挙げられ、かかるアルキレン基を有するパーフルオロアルキルアルキルアルコールとしては、2,2,2-トリフルオロエタノール(CF3CH20H)、3,3,3-トリフルオロプロパノール(CF3CH2CH2OH)、2,2,3,3,3-ペンタフルオロプロパノール(CF3CF2CH20H)、3,3,4,4,4-ペンタフルオロブタノール(CF3CF2CH2CH2OH)、2,2,3,3,4,4,5,5,5-ノナフルオロペンタノール(CF3CF2CF2CF2CH20H)、3,3,4,4,5,5,6,6,6-ノナフルオロヘキサノール(CF3CF2CF2CF2CH2CH2OH)、3,3,4,4,5,5,6,6,7,7,8,8,8-トリデカフルオロオクタノール(CF3CF2CF2CF2CF2CF2CH2CH2OH)等が例示される。Examples of the alkylene group A include —CH 2 — group, —CH 2 CH 2 — group, etc., and perfluoroalkylalkyl alcohols having such an alkylene group include 2,2,2-trifluoroethanol (CF 3 CH 2 0H), 3,3,3-trifluoro-propanol (CF 3 CH 2 CH 2 OH ), 2,2,3,3,3- pentafluoro-propanol (CF 3 CF 2 CH 2 0H ), 3,3, 4,4,4-pentafluorobutanol (CF 3 CF 2 CH 2 CH 2 OH), 2,2,3,3,4,4,5,5,5-nonafluoropentanol (CF 3 CF 2 CF 2 CF 2 CH 2 0H), 3,3,4,4,5,5,6,6,6-nonafluorohexanol (CF 3 CF 2 CF 2 CF 2 CH 2 CH 2 OH), 3,3,4, 4,5,5,6,6,7,7,8,8,8-tridecafluorooctanol (CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 2 OH) and the like are exemplified.
また、ポリフルオロアルキル基は、パーフルオロアルキル基の末端-CF3基が例えば-CF2H基などに置き換った基あるいは中間-CF2-基が-CFH-基または-CH2-基に置き換った基を指しており、かかる置換基を有する含フッ素アルコール〔I〕としては、例えば2,2,3,3-テトラフルオロプロパノール(HCF2CF2CH2OH)、2,2,3,4,4,4-ヘキサフルオロブタノール(CF3CHFCF2CH2OH)、2,2,3,3,4,4,5,5-オクタフルオロペンタノール(HCF2CF2CF2CF2CH2OH)等が挙げられる。In addition, the polyfluoroalkyl group is a group in which the terminal —CF 3 group of the perfluoroalkyl group is replaced with, for example, —CF 2 H group, or the intermediate —CF 2 — group is —CFH— group or —CH 2 — group. As the fluorinated alcohol [I] having such a substituent, for example, 2,2,3,3-tetrafluoropropanol (HCF 2 CF 2 CH 2 OH), 2,2 , 3,4,4,4-Hexafluorobutanol (CF 3 CHFCF 2 CH 2 OH), 2,2,3,3,4,4,5,5-octafluoropentanol (HCF 2 CF 2 CF 2 CF 2 CH 2 OH) and the like.
一般式〔II〕で表されるポリフルオロアルキルアルコールは、例えば特許文献3に記載されており、次のような一連の工程を経て合成される。
まず、一般式
CnF2n+1(CF2CF2)b(CH2CH2)cI
で表されるポリフルオロアルキルアイオダイド、例えば
CF3(CH2CH2)I
CF3(CH2CH2)2I
C2F5(CH2CH2)I
C2F5(CH2CH2)2I
C3F7(CH2CH2)I
C3F7(CH2CH2)2I
C4F9(CH2CH2)I
C4F9(CH2CH2)2I
C2F5(CF2CF2)(CH2CH2)I
C2F5(CF2CF2)(CH2CH2)2I
C2F5(CF2CF2)2(CH2CH2)I
C2F5(CF2CF2)2(CH2CH2)2I
C4F9(CF2CF2)(CH2CH2)I
C4F9(CF2CF2)(CH2CH2)2I
をN-メチルホルムアミド HCONH(CH3)と反応させ、ポリフルオロアルキルアルコールとそのギ酸エステルとの混合物とした後、酸触媒の存在下でそれに加水分解反応させ、ポリフルオロアルキルアルコール
CnF2n+1(CF2CF2)b(CH2CH2)cOH
を形成させる。ただし、n+2bの値は6以下である。The polyfluoroalkyl alcohol represented by the general formula [II] is described in Patent Document 3, for example, and is synthesized through the following series of steps.
First, the general formula
C n F 2n + 1 (CF 2 CF 2 ) b (CH 2 CH 2 ) c I
A polyfluoroalkyl iodide represented by, for example,
CF 3 (CH 2 CH 2 ) I
CF 3 (CH 2 CH 2 ) 2 I
C 2 F 5 (CH 2 CH 2 ) I
C 2 F 5 (CH 2 CH 2 ) 2 I
C 3 F 7 (CH 2 CH 2 ) I
C 3 F 7 (CH 2 CH 2 ) 2 I
C 4 F 9 (CH 2 CH 2 ) I
C 4 F 9 (CH 2 CH 2 ) 2 I
C 2 F 5 (CF 2 CF 2 ) (CH 2 CH 2 ) I
C 2 F 5 (CF 2 CF 2 ) (CH 2 CH 2 ) 2 I
C 2 F 5 (CF 2 CF 2 ) 2 (CH 2 CH 2 ) I
C 2 F 5 (CF 2 CF 2 ) 2 (CH 2 CH 2 ) 2 I
C 4 F 9 (CF 2 CF 2 ) (CH 2 CH 2 ) I
C 4 F 9 (CF 2 CF 2 ) (CH 2 CH 2 ) 2 I
Is reacted with N-methylformamide HCONH (CH 3 ) to form a mixture of polyfluoroalkyl alcohol and its formate, and then hydrolyzed to it in the presence of an acid catalyst to give polyfluoroalkyl alcohol.
C n F 2n + 1 (CF 2 CF 2 ) b (CH 2 CH 2 ) c OH
To form. However, the value of n + 2b is 6 or less.
含フッ素アルコール〔I〕としてはまた、RF基がパーフルオロアルキル基のフッ素原子の一部が水素原子で置換され、炭素数6以下の末端パーフルオロアルキル基および炭素数6以下のパーフルオロアルキレン基を含んで構成されるポリフルオロアルキル基であり、具体的には炭素数3〜20、好ましくは6〜10のポリフルオロアルキル基であり、Aが炭素数2〜6、好ましくは2のアルキレン基である含フッ素アルコール、例えば一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOH 〔III〕
n:1〜6、好ましくは2〜4
a:1〜4、好ましくは1
b:0〜2、好ましくは1〜2
c:1〜3、好ましくは1
で表されるポリフルオロアルキルアルコール等が用いられる。Also as the fluorine-containing alcohol (I), R F group is part of the fluorine atoms of the perfluoroalkyl group is replaced by hydrogen atoms, perfluoroalkylene having 6 or less of terminal perfluoroalkyl group and having a carbon number of 6 or less carbon atoms A polyfluoroalkyl group comprising a group, specifically a polyfluoroalkyl group having 3 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and A is an alkylene having 2 to 6 carbon atoms, preferably 2 carbon atoms A fluorine-containing alcohol as a group, for example, a general formula
C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c OH (III)
n: 1-6, preferably 2-4
a: 1 to 4, preferably 1
b: 0-2, preferably 1-2
c: 1 to 3, preferably 1
The polyfluoroalkyl alcohol represented by these is used.
一般式〔III〕で表されるポリフルオロアルキルアルコールは、特許文献3に記載されており、次のような一連の工程を経て合成される。
まず、一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cI
で表されるポリフルオロアルキルアイオダイド、例えば
CF3(CH2CF2)(CH2CH2)I
C2F5(CH2CF2)(CH2CH2)I
C2F5(CH2CF2)(CH2CH2)2I
C3F7(CH2CF2)(CH2CH2)I
C3F7(CH2CF2)(CH2CH2)2I
C4F9(CH2CF2)(CH2CH2)I
C4F9(CH2CF2)(CH2CH2)2I
C2F5(CH2CF2)(CF2CF2)(CH2CH2)I
C2F5(CH2CF2)(CF2CF2)(CH2CH2)2I
C2F5(CH2CF2)2(CF2CF2)(CH2CH2)I
C2F5(CH2CF2)2(CF2CF2)(CH2CH2)2I
C4F9(CH2CF2)(CF2CF2)(CH2CH2)I
C4F9(CH2CF2)2(CF2CF2)(CH2CH2)I
C4F9(CH2CF2)(CF2CF2)(CH2CH2)2I
C4F9(CH2CF2)2(CF2CF2)(CH2CH2)2I
をN-メチルホルムアミド HCONH(CH3)と反応させ、ポリフルオロアルキルアルコールとそのギ酸エステルとの混合物とした後、酸触媒の存在下でそれに加水分解反応させ、ポリフルオロアルキルアルコール
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOH
を形成させる。The polyfluoroalkyl alcohol represented by the general formula [III] is described in Patent Document 3, and is synthesized through the following series of steps.
First, the general formula
C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c I
A polyfluoroalkyl iodide represented by, for example,
CF 3 (CH 2 CF 2 ) (CH 2 CH 2 ) I
C 2 F 5 (CH 2 CF 2 ) (CH 2 CH 2 ) I
C 2 F 5 (CH 2 CF 2 ) (CH 2 CH 2 ) 2 I
C 3 F 7 (CH 2 CF 2 ) (CH 2 CH 2 ) I
C 3 F 7 (CH 2 CF 2 ) (CH 2 CH 2 ) 2 I
C 4 F 9 (CH 2 CF 2 ) (CH 2 CH 2 ) I
C 4 F 9 (CH 2 CF 2 ) (CH 2 CH 2 ) 2 I
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) I
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) 2 I
C 2 F 5 (CH 2 CF 2 ) 2 (CF 2 CF 2 ) (CH 2 CH 2 ) I
C 2 F 5 (CH 2 CF 2 ) 2 (CF 2 CF 2 ) (CH 2 CH 2 ) 2 I
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) I
C 4 F 9 (CH 2 CF 2 ) 2 (CF 2 CF 2 ) (CH 2 CH 2 ) I
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) 2 I
C 4 F 9 (CH 2 CF 2 ) 2 (CF 2 CF 2 ) (CH 2 CH 2 ) 2 I
Is reacted with N-methylformamide HCONH (CH 3 ) to form a mixture of polyfluoroalkyl alcohol and its formate, and then hydrolyzed to it in the presence of an acid catalyst to give polyfluoroalkyl alcohol.
C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c OH
To form.
含フッ素アルコール〔Ia〕としては、RF′基が炭素数6以下の末端パーフルオロアルキル基および炭素数6以下のパーフルオロアルキレン基を有する、O、SまたはN原子を含有する直鎖状または分岐状パーフルオロアルキル基であり、具体的には炭素数3〜305、好ましくは8〜35のO、SまたはN含有パーフルオロアルキル基であり、Aが炭素数1〜3、好ましくは1のアルキレン基である含フッ素アルコール、例えば一般式
CmF2m+1O〔CF(CF3)CF2O〕dCF(CF3)(CH2)eOH 〔IIa〕
m:1〜3、好ましくは3
d:0〜100、好ましくは1〜10
e:1〜3、好ましくは1
で表されるヘキサフルオロプロペンオキシドオリゴマーアルコール等が用いられる。As the fluorinated alcohol [Ia], the R F ′ group has a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms, a straight chain containing O, S or N atoms, or A branched perfluoroalkyl group, specifically, an O, S or N-containing perfluoroalkyl group having 3 to 305 carbon atoms, preferably 8 to 35, and A having 1 to 3 carbon atoms, preferably 1 Fluorine-containing alcohol which is an alkylene group, for example, the general formula
C m F 2m + 1 O (CF (CF 3 ) CF 2 O] d CF (CF 3 ) (CH 2 ) e OH (IIa)
m: 1-3, preferably 3
d: 0 to 100, preferably 1 to 10
e: 1 to 3, preferably 1
The hexafluoropropene oxide oligomer alcohol etc. which are represented by these are used.
また、含フッ素アルコール〔Ib〕としては、RF′′基が炭素数6以下のパーフルオロアルキレン基を有し、具体的には炭素数5〜160のO、SまたはN含有パーフルオロアルキレン基であり、Aが炭素数1〜3、好ましくは1のアルキレン基である含フッ素アルコール、例えば一般式
HO(CH2)fCF(CF3)〔OCF2CF(CF3)〕gO(CF2)hO〔CF(CF3)CF2O〕iCF(CF3)(CH2)fOH
〔IIb〕
f:1〜3、好ましくは1
g+i:0〜50、好ましくは2〜50
h:1〜6、好ましくは2
で表されるパーフルオロアルキレンエーテルジオール等が用いられる。Further, as the fluorine-containing alcohol [Ib], the R F ″ group has a perfluoroalkylene group having 6 or less carbon atoms, specifically, an O, S or N-containing perfluoroalkylene group having 5 to 160 carbon atoms. And a fluorine-containing alcohol in which A is an alkylene group having 1 to 3, preferably 1, carbon atoms, such as the general formula
HO (CH 2 ) f CF (CF 3 ) [OCF 2 CF (CF 3 )] g O (CF 2 ) h O [CF (CF 3 ) CF 2 O] i CF (CF 3 ) (CH 2 ) f OH
[IIb]
f: 1 to 3, preferably 1
g + i: 0 to 50, preferably 2 to 50
h: 1-6, preferably 2
A perfluoroalkylene ether diol represented by the formula:
一般式〔IIa〕で表されるヘキサフルオロプロペンオキシドオリゴマーアルコールにおいて、m=1、e=1の化合物は特許文献4に記載されており、次のような工程を経て合成される。
一般式 CF3O〔CF(CF3)CF2O〕nCF(CF3)COOR (R:アルキル基、n:0〜12の整数)で表される含フッ素エーテルカルボン酸アルキルエステルを、水素化ホウ素ナトリウム等の還元剤を用いて還元反応させる。In the hexafluoropropene oxide oligomer alcohol represented by the general formula [IIa], a compound having m = 1 and e = 1 is described in Patent Document 4 and synthesized through the following steps.
Fluorine-containing ether carboxylic acid alkyl ester represented by the general formula CF 3 O [CF (CF 3 ) CF 2 O] n CF (CF 3 ) COOR (R: alkyl group, n: integer of 0 to 12), hydrogen Reduction reaction is performed using a reducing agent such as sodium borohydride.
さらに、一般式〔IIb〕で表されるパーフルオロアルキレンエーテルジオールにおいて、f=1は特許文献5〜6に記載されており、次のような一連の工程を経て合成される。
FOCRfCOF → H3COOCRfCOOCH3 → HOCH2RfCH2OH
Rf:-CF(CF3)〔OCF2C(CF3)〕aO(CF2)cO〔CF(CF3)CF2O〕bCF(CF3)-Furthermore, in the perfluoroalkylene ether diol represented by the general formula [IIb], f = 1 is described in Patent Documents 5 to 6, and is synthesized through the following series of steps.
FOCR COF → H 3 COO CR COOCH 3 → HOCH 2 RfCH 2 OH
Rf: -CF (CF 3 ) [OCF 2 C (CF 3 )] a O (CF 2 ) c O [CF (CF 3 ) CF 2 O] b CF (CF 3 )-
アルコキシシランが含フッ素アルコールと共に用いられる場合には、それは一般式
(R1O)pSi(OR2)q(R3)r 〔IV〕
R1、R3:H、C1〜C6のアルキル基またはアリール基
R2:C1〜C6のアルキル基またはアリール基
ただし、R1、R2、R3が共にアリール基であることはない
p+q+r:4 ただし、qは0ではない
で表され、例えばトリメトキシシラン、トリエトキシシラン、トリメトキシメチルシラン、トリエトキシメチルシラン、トリメトキシフェニルシラン、トリエトキシフェニルシラン、テトラメトキシシラン、テトラエトキシシラン等が用いられる。When alkoxysilane is used with a fluorinated alcohol, it has the general formula
(R 1 O) p Si (OR 2 ) q (R 3 ) r (IV)
R 1, R 3: H, alkyl group or aryl group C 1 -C 6
R 2: an alkyl group or an aryl group of C 1 -C 6
However, R 1 , R 2 and R 3 are not all aryl groups
p + q + r: 4 where q is not 0, for example, trimethoxysilane, triethoxysilane, trimethoxymethylsilane, triethoxymethylsilane, trimethoxyphenylsilane, triethoxyphenylsilane, tetramethoxysilane Tetraethoxysilane or the like is used.
これらの各成分は、含フッ素アルコール100重量部に対し、ホウ酸が約0.1〜50重量部、好ましくは約10〜20重量部の割合で、またアルコキシシランが含フッ素アルコールに対して約1.0以下、好ましくは約0.05〜0.50のモル比で用いられる。ホウ酸の使用割合がこれよりも少ないと撥水撥油性が低くなり、一方これよりも多い割合で使用されると溶媒への分散性が悪くなる。また、アルコキシシランの使用割合がこれよりも多い割合で使用されると撥水撥油性が低くなる。 Each of these components is about 0.1 to 50 parts by weight, preferably about 10 to 20 parts by weight of boric acid with respect to 100 parts by weight of the fluorine-containing alcohol, and alkoxysilane is about 1.0 or less with respect to the fluorine-containing alcohol. , Preferably in a molar ratio of about 0.05 to 0.50. When the proportion of boric acid used is less than this, the water and oil repellency becomes low, while when it is used in a proportion higher than this, the dispersibility in the solvent becomes poor. Further, when the alkoxysilane is used in a proportion higher than this, the water / oil repellency is lowered.
得られた含フッ素ホウ酸コンポジット粒子中の含フッ素アルコール量は、約25〜98モル%、好ましくは約40〜70モル%であり、コンポジット粒子径(動的光散乱法により測定)は約10〜600nm、好ましくは約15〜350nmである。 The amount of fluorinated alcohol in the obtained fluorinated boric acid composite particles is about 25 to 98 mol%, preferably about 40 to 70 mol%, and the composite particle diameter (measured by dynamic light scattering method) is about 10 ˜600 nm, preferably about 15 to 350 nm.
反応生成物である含フッ素ホウ酸コンポジット粒子は、ホウ酸粒子の水酸基に含フッ素アルコールが結合しているものと考えられ、したがってホウ酸の化学的、熱的安定性とフッ素のすぐれた撥水撥油性、防汚性などが有効に発揮されており、実際にガラス表面を含フッ素ホウ酸コンポジット粒子で処理したものは良好な撥水撥油性を示している。また、含フッ素ホウ酸コンポジット粒子の粒径およびそのバラツキも小さい値を示している。なお、含フッ素ホウ酸コンポジット粒子は、含フッ素アルコールとアルコキシシランとの両者およびホウ酸粒子の反応生成物としても形成されるが、この発明の目的を阻害しない限り他の成分の混在も許容される。 Fluorine-containing boric acid composite particles, which are reaction products, are considered to have fluorine-containing alcohol bonded to the hydroxyl groups of boric acid particles. Therefore, chemical and thermal stability of boric acid and excellent water repellency of fluorine Oil repellency, antifouling properties, etc. are effectively exhibited, and the actual glass surface treated with fluorinated boric acid composite particles shows good water and oil repellency. In addition, the particle size and variation of the fluorine-containing boric acid composite particles are also small. The fluorine-containing boric acid composite particles are also formed as a reaction product of both fluorine-containing alcohol and alkoxysilane and boric acid particles, but other components can be mixed unless the object of the present invention is impaired. The
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
実施例1
CF3(CF2)5(CH2)2OH〔FA-6〕1100mg、ホウ酸200mgおよびテトラヒドロフラン〔THF〕2mlを容量30mlの反応容器に仕込み、室温条件下で1日撹拌した。その後、溶媒を留去し、目的とする含フッ素ホウ酸コンポジット粒子767mg(収率59%)を得た。得られた含フッ素ホウ酸コンポジット粒子について、次の各項目の測定を行った。
粒子径およびそのバラツキ:表1
25℃で固形分濃度1g/Lメタノール分散液について、動的光散乱(DLS)測定法によって測定
液滴の接触角(単位:°):表2
メタノール分散液(粒子濃度5g/L)を、ガラスプレパラートにディッピングし、室温条件下で乾燥させ、得られた薄膜表面にn-ドデカンまたは水の液滴4μlを静かに接触させ、付着した液滴の接触角を、θ/2法により接触角計(協和界面化学製Drop Master 300)で測定した。なお、水については経時的な測定が行われた。
各実施例でのガラス基材に対する接触角は、n-ドデカンおよび水に対しいずれも撥水性もしくは撥油性を示した。Example 1
CF 3 (CF 2 ) 5 (CH 2 ) 2 OH [FA-6] 1100 mg, boric acid 200 mg and tetrahydrofuran [THF] 2 ml were charged into a 30 ml capacity reaction vessel and stirred at room temperature for 1 day. Thereafter, the solvent was distilled off to obtain 767 mg (yield 59%) of the desired fluorine-containing boric acid composite particles. The obtained fluorine-containing boric acid composite particles were measured for the following items.
Particle size and its variation: Table 1
Measured by dynamic light scattering (DLS) measurement method for solid dispersion of 1g / L methanol at 25 ° C Droplet contact angle (unit: °): Table 2
Methanol dispersion (particle concentration 5g / L) was dipped into a glass preparation, dried at room temperature, and 4μl of n-dodecane or water droplets were gently brought into contact with the surface of the thin film. The contact angle was measured with a contact angle meter (Drop Master 300 manufactured by Kyowa Interface Chemical) by the θ / 2 method. The water was measured over time.
The contact angle with respect to the glass substrate in each example showed water repellency or oil repellency for both n-dodecane and water.
実施例2〜9
実施例1において、FA-6量、ホウ酸量がそれぞれ適宜変更された。Examples 2-9
In Example 1, the amount of FA-6 and the amount of boric acid were appropriately changed.
実施例10〜19
実施例1において、FA-6の代りに種々の含フッ素アルコールが用いられ、またテトラエトキシシラン〔TEOS;密度0.94g/cm3〕も適宜用いられた。THF量は、実施例14〜16では4ml用いられた。
OXF3PO:HOCH2CF(CF3)OCF2CF(CF3)OCF2CF2OCF(CF3)CH2OH
OXF14PO:HOCH2CF(CF3)〔OCF2CF(CF3)〕nOCF2CF2O〔CF(CF3)CF2O〕mCF(CF3)CH2OH
(n+m=12)
DTFAC:C4F9(CH2CF2)(CF2CF2)2(CH2CH2)
表2
水 (経過時間:分)
例 n-ドデカン 0 5 10 15 20 25 30
実施例1 39 62 59 57 54 55 52 50
〃 2 39 46 46 46 46 47 48 48
〃 3 31 44 40 35 27 21 14 7
〃 4 31 45 41 36 32 27 19 14
〃 5 28 54 46 41 35 29 24 16
〃 6 31 42 38 34 30 22 20 15
〃 7 33 49 46 41 32 28 19 11
〃 8 37 53 48 42 38 32 21 23
〃 9 45 98 93 88 82 71 63 48
〃 10 49 62 56 50 45 36 30 29
〃 11 20 67 65 62 60 59 56 56
〃 12 47 44 42 41 37 36 33 31
〃 13 40 25 21 19 17 16 15 14
〃 14 53 53 50 49 47 46 45 42
〃 15 53 55 56 53 50 48 47 44
〃 16 56 58 49 48 47 44 43 42
〃 17 38 77 74 69 63 57 57 60
〃 18 49 71 69 66 60 53 47 43
〃 19 50 100 93 93 86 80 80 80 Examples 10-19
In Example 1, various fluorine-containing alcohols were used in place of FA-6, and tetraethoxysilane [TEOS; density 0.94 g / cm 3 ] was also appropriately used. The amount of THF used in Examples 14 to 16 was 4 ml.
OXF3PO: HOCH 2 CF (CF 3 ) OCF 2 CF (CF 3 ) OCF 2 CF 2 OCF (CF 3 ) CH 2 OH
OXF14PO: HOCH 2 CF (CF 3 ) [OCF 2 CF (CF 3 )] n OCF 2 CF 2 O [CF (CF 3 ) CF 2 O] m CF (CF 3 ) CH 2 OH
(n + m = 12)
DTFAC: C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 )
Table 2
Water (Elapsed time: minutes)
Example n-Dodecane 0 5 10 15 20 25 30
Example 1 39 62 59 57 54 55 52 50
〃 2 39 46 46 46 46 47 48 48
〃 3 31 44 40 35 27 21 14 7
4 4 31 45 41 36 32 27 19 14
5 5 28 54 46 41 35 29 24 16
6 6 31 42 38 34 30 22 20 15
7 7 33 49 46 41 32 28 19 11
37 8 37 53 48 42 38 32 21 23
9 9 45 98 93 88 82 71 63 48
〃 10 49 62 56 50 45 36 30 29
〃 11 20 67 65 62 60 59 56 56
〃 12 47 44 42 41 37 36 33 31
〃 13 40 25 21 19 17 16 15 14
〃 14 53 53 50 49 47 46 45 42
〃 15 53 55 56 53 50 48 47 44
〃 16 56 58 49 48 47 44 43 42
〃 17 38 77 74 69 63 57 57 60
〃 18 49 71 69 66 60 53 47 43
〃 19 50 100 93 93 86 80 80 80
比較例1
コーティングされていないガラス基材について、実施例1と同様に液滴の接触角測定が行われた。Comparative Example 1
For the uncoated glass substrate, the contact angle of the droplet was measured in the same manner as in Example 1.
比較例2
ホウ酸を用いてコーティングされたガラス基材について、実施例1と同様に液滴の接触角測定が行われた。Comparative Example 2
For the glass substrate coated with boric acid, the contact angle of the droplet was measured in the same manner as in Example 1.
比較例3〜7
実施例1の液滴の接触角測定において、含フッ素ホウ酸コンポジット粒子メタノール分散液の代わりに下記試料のメタノール分散液(5g/L)を用いてコーティングされたガラス基材が用いられた。
比較例3:ホウ酸/TEOS
比較例4:FA-6
比較例5:FA-6/TEOS
比較例6:OXF3PO
比較例7:OXF14PO
ただし、比較例3では、実施例1においてFA-6が用いられず、ホウ酸50mg(0.81ミリモル)、TEOS 0.10ml(0.45ミリモル)が用いられ、生成物の収量は130mg、収率は90%であった。また、比較例5では、実施例1においてホウ酸が用いられず、FA-6 1100mg(3.02ミリモル)、TEOS 0.10ml(0.45ミリモル)が用いられ、生成物の収量は763mg、収率は68%であった。Comparative Examples 3-7
In the measurement of the contact angle of the droplets of Example 1, a glass substrate coated with the following sample methanol dispersion (5 g / L) was used instead of the fluorine-containing boric acid composite particle methanol dispersion.
Comparative Example 3: Boric acid / TEOS
Comparative Example 4: FA-6
Comparative Example 5: FA-6 / TEOS
Comparative Example 6: OXF3PO
Comparative Example 7: OXF14PO
However, in Comparative Example 3, FA-6 was not used in Example 1, but 50 mg (0.81 mmol) of boric acid and 0.10 ml (0.45 mmol) of TEOS were used. The yield of the product was 130 mg and the yield was 90%. Met. In Comparative Example 5, boric acid was not used in Example 1, but FA-6 1100 mg (3.02 mmol) and TEOS 0.10 ml (0.45 mmol) were used. The yield of the product was 763 mg, and the yield was 68%. Met.
以上の各比較例で得られた結果は、次の表3に示される。
表3
水 (経過時間:分)
例 n-ドデカン 0 5 10 15 20 25 30
比較例1 0 50 − − − − − −
〃 2 22 66 − − − − − −
〃 3 20 55 − − − − − −
〃 4 30 43 39 35 31 22 21 16
〃 5 11 36 32 28 21 17 13 7
〃 6 45 62 60 58 56 55 50 53
〃 7 58 63 54 51 49 47 45 42
The results obtained in the above comparative examples are shown in the following Table 3.
Table 3
Water (Elapsed time: minutes)
Example n-Dodecane 0 5 10 15 20 25 30
Comparative Example 1 0 50 − − − − − −
〃 2 22 66 − − − − − −
3 3 20 55 − − − − − −
4 4 30 43 39 35 31 22 21 16
11 5 11 36 32 28 21 17 13 7
6 6 45 62 60 58 56 55 50 53
〃 7 58 63 54 51 49 47 45 42
本発明の目的は、環境中に放出されてもパーフルオロオクタン酸等を生成させず、しかも短鎖の化合物に分解され易いユニットを有する含フッ素アルコールを用い、無機質基材等に良好な撥水性および撥油性を付与する含フッ素ホウ酸コンポジット粒子を提供することにある。 An object of the present invention is to use a fluorine-containing alcohol having a unit that does not generate perfluorooctanoic acid or the like even when released into the environment and is easily decomposed into a short-chain compound, and has good water repellency on an inorganic substrate or the like Another object is to provide fluorine-containing boric acid composite particles that impart oil repellency .
また、本発明によって、一般式
RF′-A-OH 〔Ia〕
または一般式
HO-A-RF′′-A-OH 〔Ib〕
(ここで、RF′は炭素数6以下の末端パーフルオロアルキル基および炭素数6以下のパーフルオロアルキレン基を有する、O原子を含有する直鎖状または分岐状パーフルオロアルキル基であり、RF′′は炭素数6以下のパーフルオロアルキレン基を有する、O原子を含有する直鎖状または分岐状のパーフルオロアルキレン基であり、Aは炭素数1〜6のアルキレン基である)で表される含フッ素アルコールとホウ酸との縮合体からなる含フッ素ホウ酸コンポジット粒子が提供される。含フッ素ホウ酸コンポジット粒子は、含フッ素アルコール〔Ia〕または〔Ib〕とこれら含フッ素アルコールに対してモル比1.0以下のアルコキシシランとの両者およびホウ酸の縮合体であってもよい。
Also, according to the invention, the general formula
R F ′ -A-OH (Ia)
Or general formula
HO-AR F ′ ′ -A-OH (Ib)
(Wherein R F ′ is a linear or branched perfluoroalkyl group containing an O atom having a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms , and R F '' is a linear or branched perfluoroalkylene group having a perfluoroalkylene group having 6 or less carbon atoms and containing an O atom , and A is an alkylene group having 1 to 6 carbon atoms). Fluorine-containing boric acid composite particles comprising a condensate of fluorine-containing alcohol and boric acid are provided. The fluorine-containing boric acid composite particles may be a condensate of both fluorine-containing alcohol [Ia] or [Ib] and an alkoxysilane having a molar ratio of 1.0 or less with respect to these fluorine-containing alcohols and boric acid.
含フッ素アルコール〔Ia〕としては、RF′基が炭素数6以下の末端パーフルオロアルキル基および炭素数6以下のパーフルオロアルキレン基を有する、O原子を含有する直鎖状または分岐状パーフルオロアルキル基であり、具体的には炭素数3〜305、好ましくは8〜35のO含有パーフルオロアルキル基であり、Aが炭素数1〜3、好ましくは1のアルキレン基である含フッ素アルコール、例えば一般式
CmF2m+1O〔CF(CF3)CF2O〕dCF(CF3)(CH2)eOH 〔IIa〕
m:1〜3、好ましくは3
d:0〜100、好ましくは1〜10
e:1〜3、好ましくは1
で表されるヘキサフルオロプロペンオキシドオリゴマーアルコール等が用いられる。
As the fluorine-containing alcohol [Ia], the R F ′ group has a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms, and a linear or branched perfluoro having an O atom A fluorine-containing alcohol which is an alkyl group, specifically an O-containing perfluoroalkyl group having 3 to 305 carbon atoms, preferably 8 to 35, and A is an alkylene group having 1 to 3 carbon atoms, preferably 1. For example, the general formula
C m F 2m + 1 O (CF (CF 3 ) CF 2 O] d CF (CF 3 ) (CH 2 ) e OH (IIa)
m: 1-3, preferably 3
d: 0 to 100, preferably 1 to 10
e: 1 to 3, preferably 1
The hexafluoropropene oxide oligomer alcohol etc. which are represented by these are used.
また、含フッ素アルコール〔Ib〕としては、RF′′基が炭素数6以下のパーフルオロアルキレン基を有し、具体的には炭素数5〜160のO含有パーフルオロアルキレン基であり、Aが炭素数1〜3、好ましくは1のアルキレン基である含フッ素アルコール、例えば一般式
HO(CH2)fCF(CF3)〔OCF2CF(CF3)〕gO(CF2)hO〔CF(CF3)CF2O〕iCF(CF3)(CH2)fOH
〔IIb〕
f:1〜3、好ましくは1
g+i:0〜50、好ましくは2〜50
h:1〜6、好ましくは2
で表されるパーフルオロアルキレンエーテルジオール等が用いられる。
Further, as the fluorinated alcohol [Ib], the R F ″ group has a perfluoroalkylene group having 6 or less carbon atoms, specifically, an O-containing perfluoroalkylene group having 5 to 160 carbon atoms, and A Is a fluorine-containing alcohol having 1 to 3 carbon atoms, preferably 1 alkylene group, for example
HO (CH 2 ) f CF (CF 3 ) [OCF 2 CF (CF 3 )] g O (CF 2 ) h O [CF (CF 3 ) CF 2 O] i CF (CF 3 ) (CH 2 ) f OH
[IIb]
f: 1 to 3, preferably 1
g + i: 0 to 50, preferably 2 to 50
h: 1-6, preferably 2
A perfluoroalkylene ether diol represented by the formula:
実施例10〜19
実施例1において、FA-6の代りに種々の含フッ素アルコールが用いられ、またテトラエトキシシラン〔TEOS;密度0.94g/cm3〕も適宜用いられた。THF量は、実施例14〜16では4ml用いられた。
OXF3PO:HOCH2CF(CF3)OCF2CF(CF3)OCF2CF2OCF(CF3)CH2OH
OXF14PO:HOCH2CF(CF3)〔OCF2CF(CF3)〕nOCF2CF2O〔CF(CF3)CF2O〕mCF(CF3)CH2OH
(n+m=12)
DTFAC:C4F9(CH2CF2)(CF2CF2)2(CH2CH2)OH
表2
水 (経過時間:分)
例 n-ドデカン 0 5 10 15 20 25 30
実施例1 39 62 59 57 54 55 52 50
〃 2 39 46 46 46 46 47 48 48
〃 3 31 44 40 35 27 21 14 7
〃 4 31 45 41 36 32 27 19 14
〃 5 28 54 46 41 35 29 24 16
〃 6 31 42 38 34 30 22 20 15
〃 7 33 49 46 41 32 28 19 11
〃 8 37 53 48 42 38 32 21 23
〃 9 45 98 93 88 82 71 63 48
〃 10 49 62 56 50 45 36 30 29
〃 11 20 67 65 62 60 59 56 56
〃 12 47 44 42 41 37 36 33 31
〃 13 40 25 21 19 17 16 15 14
〃 14 53 53 50 49 47 46 45 42
〃 15 53 55 56 53 50 48 47 44
〃 16 56 58 49 48 47 44 43 42
〃 17 38 77 74 69 63 57 57 60
〃 18 49 71 69 66 60 53 47 43
〃 19 50 100 93 93 86 80 80 80
Examples 10-19
In Example 1, various fluorine-containing alcohols were used in place of FA-6, and tetraethoxysilane [TEOS; density 0.94 g / cm 3 ] was also appropriately used. The amount of THF used in Examples 14 to 16 was 4 ml.
OXF3PO: HOCH 2 CF (CF 3 ) OCF 2 CF (CF 3 ) OCF 2 CF 2 OCF (CF 3 ) CH 2 OH
OXF14PO: HOCH 2 CF (CF 3 ) [OCF 2 CF (CF 3 )] n OCF 2 CF 2 O [CF (CF 3 ) CF 2 O] m CF (CF 3 ) CH 2 OH
(n + m = 12)
DTFAC: C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) OH
Table 2
Water (Elapsed time: minutes)
Example n-Dodecane 0 5 10 15 20 25 30
Example 1 39 62 59 57 54 55 52 50
〃 2 39 46 46 46 46 47 48 48
〃 3 31 44 40 35 27 21 14 7
4 4 31 45 41 36 32 27 19 14
5 5 28 54 46 41 35 29 24 16
6 6 31 42 38 34 30 22 20 15
7 7 33 49 46 41 32 28 19 11
37 8 37 53 48 42 38 32 21 23
9 9 45 98 93 88 82 71 63 48
〃 10 49 62 56 50 45 36 30 29
〃 11 20 67 65 62 60 59 56 56
〃 12 47 44 42 41 37 36 33 31
〃 13 40 25 21 19 17 16 15 14
〃 14 53 53 50 49 47 46 45 42
〃 15 53 55 56 53 50 48 47 44
〃 16 56 58 49 48 47 44 43 42
〃 17 38 77 74 69 63 57 57 60
〃 18 49 71 69 66 60 53 47 43
〃 19 50 100 93 93 86 80 80 80
本発明は、含フッ素ホウ酸コンポジット粒子に関する。さらに詳しくは、表面処理特性を改善せしめた含フッ素ホウ酸コンポジット粒子に関する。 The present invention relates to fluorine-containing boric acid composite particles. More specifically, the present invention relates to fluorine-containing boric acid composite particles having improved surface treatment characteristics.
無機材料表面を各種の化合物やポリマーでコーティングすることにより、様々な表面特性を発現させることが知られている。中でも、フッ素系化合物を表面処理に使用した場合には、フッ素原子の有する特性から、撥水性だけではなく撥油性の点でも表面改質できるので、様々な基材へのコーティングに利用されている。 It is known that various surface characteristics are expressed by coating the surface of an inorganic material with various compounds and polymers. In particular, when fluorine-based compounds are used for surface treatment, the surface properties can be modified not only for water repellency but also for oil repellency because of the properties of fluorine atoms, so they are used for coating on various substrates. .
特に、C8のパーフルオロアルキル基を有する表面処理剤を基質に塗布するとことで、高い撥水撥油性を示すコーティングが可能であるが、近年C7以上のパーフルオロアルキル基を有する化合物が、細胞株を用いた試験管内試験において、発がん因子と考えられている細胞間コミュニケーション阻害をひき起すこと、かつこの阻害は官能基ではなく、フッ素化された炭素鎖長に依存し、炭素鎖が長いもの程阻害力が高いことが報告されており、フッ素化された炭素数の長い化合物を使用したモノマーの製造が制限されるようになってきている。 In particular, by applying a surface treatment agent having a C 8 perfluoroalkyl group to a substrate, a coating showing high water and oil repellency is possible, but in recent years, a compound having a C 7 or more perfluoroalkyl group has In vitro tests using cell lines cause intercellular communication inhibition, which is considered to be a carcinogenic factor, and this inhibition is not a functional group but depends on the fluorinated carbon chain length, and the carbon chain is long It has been reported that the higher the inhibition power, the more limited the production of monomers using fluorinated compounds with a long carbon number.
また、炭素数が6以下のパーフルオロアルキル基を有する含フッ素アルコールにあっては、ガラス、金属、石材等の無機質基材への密着性に欠けるという問題もみられる。 In addition, the fluorine-containing alcohol having a perfluoroalkyl group having 6 or less carbon atoms has a problem that it lacks adhesion to an inorganic base material such as glass, metal, and stone.
特許文献1〜2には、含フッ素アルコール、アルコキシシラン(および重合性官能基含有アルコール)を縮合反応させることが記載されているが、得られたアルコキシシラン誘導体は、光酸発生剤または光塩基発生剤を添加した硬化性組成物、あるいは無機導電塗料組成物の調製に用いられている。 Patent Documents 1 and 2 describe that a fluorine-containing alcohol and an alkoxysilane (and a polymerizable functional group-containing alcohol) are subjected to a condensation reaction. The obtained alkoxysilane derivative is a photoacid generator or a photobase. It is used for the preparation of a curable composition to which a generator is added, or an inorganic conductive coating composition.
本発明の目的は、環境中に放出されてもパーフルオロオクタン酸等を生成させず、しかも短鎖の化合物に分解され易いユニットを有する含フッ素アルコールを用い、無機質基材等に良好な撥水性および撥油性を付与する含フッ素ホウ酸コンポジット粒子を提供することにある。 An object of the present invention is to use a fluorine-containing alcohol having a unit that does not generate perfluorooctanoic acid or the like even when released into the environment and is easily decomposed into a short-chain compound, and has good water repellency on an inorganic substrate or the like. Another object is to provide fluorine-containing boric acid composite particles that impart oil repellency.
本発明によって、一般式
C n F 2n+1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c OH 〔I〕
(ここで、nは1〜6、aは1〜4、bは0〜2、cは1〜3の整数である)で表される含フッ素アルコールとホウ酸との縮合体からなる含フッ素ホウ酸コンポジット粒子が提供される。含フッ素ホウ酸コンポジット粒子は、含フッ素アルコール〔I〕と含フッ素アルコールに対してモル比1.0以下のアルコキシシランとの両者およびホウ酸の縮合体であってもよい。
According to the invention, the general formula
C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c OH (I)
(Wherein n is 1 to 6, a is 1 to 4, b is an integer of 0 to 2, and c is an integer of 1 to 3) Fluorine-containing fluorine-containing condensate Boric acid composite particles are provided. The fluorine-containing boric acid composite particles may be a condensate of both a fluorine-containing alcohol [I] and an alkoxysilane having a molar ratio of 1.0 or less with respect to the fluorine-containing alcohol and boric acid.
また、本発明によって、一般式
C m F 2m+1 O〔CF(CF 3 )CF 2 O〕 d CF(CF 3 )(CH 2 ) e OH 〔Ia〕
(ここで、mは1〜3、dは0〜100、eは1〜3の整数である)で表されるヘキサフルオロプロペンオキシドオリゴマーアルコール
または一般式
HO(CH 2 ) f CF(CF 3 )〔OCF 2 CF(CF 3 )〕 g O(CF 2 ) h O〔CF(CF 3 )CF 2 O〕 i
CF(CF 3 )(CH 2 ) f OH 〔Ib〕
(ここで、fは1〜3、g+iは0〜50、hは1〜6の整数である)で表されるパーフルオロアルキレンエーテルジオール
である含フッ素アルコールとホウ酸との縮合体からなる含フッ素ホウ酸コンポジット粒子が提供される。含フッ素ホウ酸コンポジット粒子は、含フッ素アルコール〔Ia〕または〔Ib〕とこれら含フッ素アルコールに対してモル比1.0以下のアルコキシシランとの両者およびホウ酸の縮合体であってもよい。
Also, according to the invention, the general formula
C m F 2m + 1 O (CF (CF 3 ) CF 2 O] d CF (CF 3 ) (CH 2 ) e OH (Ia)
(Where m is 1 to 3, d is 0 to 100, and e is an integer of 1 to 3)
Or general formula
HO (CH 2 ) f CF (CF 3 ) [OCF 2 CF (CF 3 )] g O (CF 2 ) h O [CF (CF 3 ) CF 2 O] i
CF (CF 3 ) (CH 2 ) f OH (Ib)
(Where f is 1 to 3, g + i is 0 to 50, and h is an integer of 1 to 6).
Consisting condensate of fluorine-containing alcohol and boric acid fluorinated borate composite particles is provided at. The fluorine-containing boric acid composite particles may be a condensate of both fluorine-containing alcohol [Ia] or [Ib] and an alkoxysilane having a molar ratio of 1.0 or less with respect to these fluorine-containing alcohols and boric acid.
本発明で用いられる含フッ素アルコールは、末端パーフルオロアルキル基やポリフルオロアルキル基中のパーフルオロアルキレン鎖の炭素数が6以下のものであり、短鎖の含フッ素化合物に分解され易いユニットを有しているため、環境汚染につながらない。また、得られた含フッ素ホウ酸コンポジット粒子は、基材表面に良好な撥水撥油性、防汚機能性を示す薄膜を形成させ、この薄膜は無機質基材等に対する密着性にもすぐれている。 The fluorine-containing alcohol used in the present invention has a perfluoroalkylene chain having 6 or less carbon atoms in the terminal perfluoroalkyl group or polyfluoroalkyl group, and has a unit that is easily decomposed into a short-chain fluorine-containing compound. Therefore, it does not lead to environmental pollution. In addition, the obtained fluorinated boric acid composite particles form a thin film having good water / oil repellency and antifouling function on the surface of the substrate, and this thin film has excellent adhesion to an inorganic substrate or the like. .
含フッ素アルコール〔I〕としては、一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOH
n:1〜6、好ましくは2〜4
a:1〜4、好ましくは1
b:0〜2、好ましくは1〜2
c:1〜3、好ましくは1
で表されるポリフルオロアルキルアルコールが用いられる。
As fluorine-containing alcohol [I], general formula
C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c OH
n: 1-6, preferably 2-4
a: 1 to 4, preferably 1
b: 0-2, preferably 1-2
c: 1 to 3, preferably 1
The polyfluoroalkyl alcohol represented by these is used.
一般式〔I〕で表されるポリフルオロアルキルアルコールは、特許文献3に記載されており、次のような一連の工程を経て合成される。
まず、一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cI
で表されるポリフルオロアルキルアイオダイド、例えば
CF3(CH2CF2)(CH2CH2)I
C2F5(CH2CF2)(CH2CH2)I
C2F5(CH2CF2)(CH2CH2)2I
C3F7(CH2CF2)(CH2CH2)I
C3F7(CH2CF2)(CH2CH2)2I
C4F9(CH2CF2)(CH2CH2)I
C4F9(CH2CF2)(CH2CH2)2I
C2F5(CH2CF2)(CF2CF2)(CH2CH2)I
C2F5(CH2CF2)(CF2CF2)(CH2CH2)2I
C2F5(CH2CF2)2(CF2CF2)(CH2CH2)I
C2F5(CH2CF2)2(CF2CF2)(CH2CH2)2I
C4F9(CH2CF2)(CF2CF2)(CH2CH2)I
C4F9(CH2CF2)2(CF2CF2)(CH2CH2)I
C4F9(CH2CF2)(CF2CF2)(CH2CH2)2I
C4F9(CH2CF2)2(CF2CF2)(CH2CH2)2I
をN-メチルホルムアミド HCONH(CH3)と反応させ、ポリフルオロアルキルアルコールとそのギ酸エステルとの混合物とした後、酸触媒の存在下でそれに加水分解反応させ、ポリフルオロアルキルアルコール
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOH
を形成させる。
The polyfluoroalkyl alcohol represented by the general formula [I] is described in Patent Document 3 and synthesized through the following series of steps.
First, the general formula
C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c I
A polyfluoroalkyl iodide represented by, for example,
CF 3 (CH 2 CF 2 ) (CH 2 CH 2 ) I
C 2 F 5 (CH 2 CF 2 ) (CH 2 CH 2 ) I
C 2 F 5 (CH 2 CF 2 ) (CH 2 CH 2 ) 2 I
C 3 F 7 (CH 2 CF 2 ) (CH 2 CH 2 ) I
C 3 F 7 (CH 2 CF 2 ) (CH 2 CH 2 ) 2 I
C 4 F 9 (CH 2 CF 2 ) (CH 2 CH 2 ) I
C 4 F 9 (CH 2 CF 2 ) (CH 2 CH 2 ) 2 I
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) I
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) 2 I
C 2 F 5 (CH 2 CF 2 ) 2 (CF 2 CF 2 ) (CH 2 CH 2 ) I
C 2 F 5 (CH 2 CF 2 ) 2 (CF 2 CF 2 ) (CH 2 CH 2 ) 2 I
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) I
C 4 F 9 (CH 2 CF 2 ) 2 (CF 2 CF 2 ) (CH 2 CH 2 ) I
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) 2 I
C 4 F 9 (CH 2 CF 2 ) 2 (CF 2 CF 2 ) (CH 2 CH 2 ) 2 I
Is reacted with N-methylformamide HCONH (CH 3 ) to form a mixture of polyfluoroalkyl alcohol and its formate, and then hydrolyzed to it in the presence of an acid catalyst to give polyfluoroalkyl alcohol.
C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c OH
To form.
含フッ素アルコール〔Ia〕としては、一般式
CmF2m+1O〔CF(CF3)CF2O〕dCF(CF3)(CH2)eOH
m:1〜3、好ましくは3
d:0〜100、好ましくは1〜10
e:1〜3、好ましくは1
で表されるヘキサフルオロプロペンオキシドオリゴマーアルコールが用いられる。
The fluorine-containing alcohol [Ia] has a general formula
C m F 2m + 1 O [CF (CF 3 ) CF 2 O] d CF (CF 3 ) (CH 2 ) e OH
m: 1-3, preferably 3
d: 0 to 100, preferably 1 to 10
e: 1 to 3, preferably 1
The hexafluoropropene oxide oligomer alcohol represented by these is used.
また、含フッ素アルコール〔Ib〕としては、一般式
HO(CH2)fCF(CF3)〔OCF2CF(CF3)〕gO(CF2)hO〔CF(CF3)CF2O〕iCF(CF3)(CH2)fOH
f:1〜3、好ましくは1
g+i:0〜50、好ましくは2〜50
h:1〜6、好ましくは2
で表されるパーフルオロアルキレンエーテルジオールが用いられる。
In addition, the fluorine-containing alcohol [Ib] has a general formula
HO (CH 2 ) f CF (CF 3 ) [OCF 2 CF (CF 3 )] g O (CF 2 ) h O [CF (CF 3 ) CF 2 O] i CF (CF 3 ) (CH 2 ) f OH
f: 1 to 3, preferably 1
g + i: 0 to 50, preferably 2 to 50
h: 1-6, preferably 2
The perfluoroalkylene ether diol represented by these is used.
一般式〔Ia〕で表されるヘキサフルオロプロペンオキシドオリゴマーアルコールにおいて、m=1、e=1の化合物は特許文献4に記載されており、次のような工程を経て合成される。
一般式 CF3O〔CF(CF3)CF2O〕nCF(CF3)COOR (R:アルキル基、n:0〜12の整数)で表される含フッ素エーテルカルボン酸アルキルエステルを、水素化ホウ素ナトリウム等の還元剤を用いて還元反応させる。
In the hexafluoropropene oxide oligomer alcohol represented by the general formula [Ia] , compounds with m = 1 and e = 1 are described in Patent Document 4 and synthesized through the following steps.
Fluorine-containing ether carboxylic acid alkyl ester represented by the general formula CF 3 O [CF (CF 3 ) CF 2 O] n CF (CF 3 ) COOR (R: alkyl group, n: integer of 0 to 12), hydrogen Reduction reaction is performed using a reducing agent such as sodium borohydride.
さらに、一般式〔Ib〕で表されるパーフルオロアルキレンエーテルジオールにおいて、f=1は特許文献5〜6に記載されており、次のような一連の工程を経て合成される。
FOCRfCOF → H3COOCRfCOOCH3 → HOCH2RfCH2OH
Rf:-CF(CF3)〔OCF2C(CF3)〕aO(CF2)cO〔CF(CF3)CF2O〕bCF(CF3)-
Furthermore, in the perfluoroalkylene ether diol represented by the general formula [Ib] , f = 1 is described in Patent Documents 5 to 6, and synthesized through the following series of steps.
FOCR COF → H 3 COO CR COOCH 3 → HOCH 2 RfCH 2 OH
Rf: -CF (CF 3 ) [OCF 2 C (CF 3 )] a O (CF 2 ) c O [CF (CF 3 ) CF 2 O] b CF (CF 3 )-
アルコキシシランが含フッ素アルコールと共に用いられる場合には、それは一般式
(R1O)pSi(OR2)q(R3)r 〔IV〕
R1、R3:H、C1〜C6のアルキル基またはアリール基
R2:C1〜C6のアルキル基またはアリール基
ただし、R1、R2、R3が共にアリール基であることはない
p+q+r:4 ただし、qは0ではない
で表され、例えばトリメトキシシラン、トリエトキシシラン、トリメトキシメチルシラン、トリエトキシメチルシラン、トリメトキシフェニルシラン、トリエトキシフェニルシラン、テトラメトキシシラン、テトラエトキシシラン等が用いられる。
When alkoxysilane is used with a fluorinated alcohol, it has the general formula
(R 1 O) p Si (OR 2 ) q (R 3 ) r (IV)
R 1, R 3: H, alkyl group or aryl group C 1 -C 6
R 2: an alkyl group or an aryl group of C 1 -C 6
However, R 1 , R 2 and R 3 are not all aryl groups
p + q + r: 4 where q is not 0, for example, trimethoxysilane, triethoxysilane, trimethoxymethylsilane, triethoxymethylsilane, trimethoxyphenylsilane, triethoxyphenylsilane, tetramethoxysilane Tetraethoxysilane or the like is used.
これらの各成分は、含フッ素アルコール100重量部に対し、ホウ酸が約0.1〜50重量部、好ましくは約10〜20重量部の割合で、またアルコキシシランが含フッ素アルコールに対して約1.0以下、好ましくは約0.05〜0.50のモル比で用いられる。ホウ酸の使用割合がこれよりも少ないと撥水撥油性が低くなり、一方これよりも多い割合で使用されると溶媒への分散性が悪くなる。また、アルコキシシランの使用割合がこれよりも多い割合で使用されると撥水撥油性が低くなる。 Each of these components is about 0.1 to 50 parts by weight, preferably about 10 to 20 parts by weight of boric acid with respect to 100 parts by weight of the fluorine-containing alcohol, and alkoxysilane is about 1.0 or less with respect to the fluorine-containing alcohol. , Preferably in a molar ratio of about 0.05 to 0.50. When the proportion of boric acid used is less than this, the water and oil repellency becomes low, while when it is used in a proportion higher than this, the dispersibility in the solvent becomes poor. Further, when the alkoxysilane is used in a proportion higher than this, the water / oil repellency is lowered.
得られた含フッ素ホウ酸コンポジット粒子中の含フッ素アルコール量は、約25〜98モル%、好ましくは約40〜70モル%であり、コンポジット粒子径(動的光散乱法により測定)は約10〜600nm、好ましくは約15〜350nmである。 The amount of fluorinated alcohol in the obtained fluorinated boric acid composite particles is about 25 to 98 mol%, preferably about 40 to 70 mol%, and the composite particle diameter (measured by dynamic light scattering method) is about 10 ˜600 nm, preferably about 15 to 350 nm.
反応生成物である含フッ素ホウ酸コンポジット粒子は、ホウ酸粒子の水酸基に含フッ素アルコールが結合しているものと考えられ、したがってホウ酸の化学的、熱的安定性とフッ素のすぐれた撥水撥油性、防汚性などが有効に発揮されており、実際にガラス表面を含フッ素ホウ酸コンポジット粒子で処理したものは良好な撥水撥油性を示している。また、含フッ素ホウ酸コンポジット粒子の粒径およびそのバラツキも小さい値を示している。なお、含フッ素ホウ酸コンポジット粒子は、含フッ素アルコールとアルコキシシランとの両者およびホウ酸粒子の反応生成物としても形成されるが、この発明の目的を阻害しない限り他の成分の混在も許容される。 Fluorine-containing boric acid composite particles, which are reaction products, are considered to have fluorine-containing alcohol bonded to the hydroxyl groups of boric acid particles. Therefore, chemical and thermal stability of boric acid and excellent water repellency of fluorine Oil repellency, antifouling properties, etc. are effectively exhibited, and the actual glass surface treated with fluorinated boric acid composite particles shows good water and oil repellency. In addition, the particle size and variation of the fluorine-containing boric acid composite particles are also small. The fluorine-containing boric acid composite particles are also formed as a reaction product of both fluorine-containing alcohol and alkoxysilane and boric acid particles, but other components can be mixed unless the object of the present invention is impaired. The
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
実施例1
HOCH 2 CF(CF 3 )OCF 2 CF(CF 3 )OCF 2 CF 2 OCF(CF 3 )CH 2 OH〔OXF3PO〕1250mg、ホウ酸60mgおよびテトラヒドロフラン〔THF〕2mlを容量30mlの反応容器に仕込み、室温条件下で1日撹拌した。その後、溶媒を留去し、目的とする含フッ素ホウ酸コンポジット粒子1061mg(収率81%)を得た。得られた含フッ素ホウ酸コンポジット粒子について、次の各項目の測定を行った。
粒子径およびそのバラツキ:表1
25℃で固形分濃度1g/Lメタノール分散液について、動的光散乱(DLS)測定法によって測定
液滴の接触角(単位:°):表2
メタノール分散液(粒子濃度5g/L)を、ガラスプレパラートにディッピングし、室温条件下で乾燥させ、得られた薄膜表面にn-ドデカンまたは水の液滴4μlを静かに接触させ、付着した液滴の接触角を、θ/2法により接触角計(協和界面化学製Drop Master 300)で測定した。なお、水については経時的な測定が行われた。
各実施例でのガラス基材に対する接触角は、n-ドデカンおよび水に対しいずれも撥水性もしくは撥油性を示した。
Example 1
HOCH 2 CF (CF 3 ) OCF 2 CF (CF 3 ) OCF 2 CF 2 OCF (CF 3 ) CH 2 OH [OXF3PO] 1250 mg, boric acid 60 mg and tetrahydrofuran [THF] 2 ml are charged into a 30 ml capacity reaction vessel. The mixture was stirred at room temperature for 1 day. Thereafter, the solvent was distilled off to obtain 1061 mg (yield 81 %) of the target fluorine-containing boric acid composite particles. The obtained fluorine-containing boric acid composite particles were measured for the following items.
Particle size and its variation: Table 1
Measured by dynamic light scattering (DLS) measurement method for solid dispersion of 1g / L methanol at 25 ° C Droplet contact angle (unit: °): Table 2
Methanol dispersion (particle concentration 5g / L) was dipped into a glass preparation, dried at room temperature, and 4μl of n-dodecane or water droplets were gently brought into contact with the surface of the thin film. The contact angle was measured with a contact angle meter (Drop Master 300 manufactured by Kyowa Interface Chemical) by the θ / 2 method. The water was measured over time.
The contact angle with respect to the glass substrate in each example showed water repellency or oil repellency for both n-dodecane and water.
実施例2〜10
実施例1において、OXF3PO量およびホウ酸量が種々変更され、あるいはOXF3POの代りに種々の含フッ素アルコールが用いられ、またテトラエトキシシラン〔TEOS;密度0.94g/cm3〕も適宜用いられた。THF量は、実施例5〜7では4ml用いられた。
OXF3PO:HOCH2CF(CF3)OCF2CF(CF3)OCF2CF2OCF(CF3)CH2OH
OXF14PO:HOCH2CF(CF3)〔OCF2CF(CF3)〕nOCF2CF2O〔CF(CF3)CF2O〕mCF(CF3)CH2OH
(n+m=12)
DTFAC:C4F9(CH2CF2)(CF2CF2)2(CH2CH2)OH
表1
含フッ素アルコール ホウ酸 TEOS 収量 収率 粒子径
実施例 略号 mg mM (mg) ml mM (mg) (%) (nm)
1 OXF3PO 1250 2.23 60 − − 1061 81 313.0±46.0
2 OXF3PO 1250 2.23 30 − − 1152 90 288.0±78.0
3 OXF3PO 5600 10.0 30 0.05 0.23 1011 79 266.0±30.0
4 OXF3PO 1250 2.23 60 0.10 0.45 1166 89 65.7± 8.9
5 OXF14PO 1000 0.42 6.5 − − 393 39 128.0±14.0
6 OXF14PO 1000 0.42 13 − − 365 36 262.0±59.0
7 OXF14PO 1000 0.42 26 − − 349 34 15.7± 1.0
8 DTFAC 100 0.19 12 − − 108 96 105.0±25.0
9 DTFAC 100 0.19 5.9 − − 103 97 10.8± 1.1
10 DTFAC 100 0.19 2.9 − − 99 96 313.0±78.0
表2
水 (経過時間:分)
例 n-ドデカン 0 5 10 15 20 25 30
実施例1 49 62 56 50 45 36 30 29
〃 2 20 67 65 62 60 59 56 56
〃 3 47 44 42 41 37 36 33 31
〃 4 40 25 21 19 17 16 15 14
〃 5 53 53 50 49 47 46 45 42
〃 6 53 55 56 53 50 48 47 44
〃 7 56 58 49 48 47 44 43 42
〃 8 38 77 74 69 63 57 57 60
〃 9 49 71 69 66 60 53 47 43
〃 10 50 100 93 93 86 80 80 80
Examples 2-10
In Example 1, the amounts of OXF3PO and boric acid were variously changed, or various fluorinated alcohols were used in place of OXF3PO , and tetraethoxysilane [TEOS; density 0.94 g / cm 3 ] was also appropriately used. The amount of THF used in Examples 5 to 7 was 4 ml.
OXF3PO: HOCH 2 CF (CF 3 ) OCF 2 CF (CF 3 ) OCF 2 CF 2 OCF (CF 3 ) CH 2 OH
OXF14PO: HOCH 2 CF (CF 3 ) [OCF 2 CF (CF 3 )] n OCF 2 CF 2 O [CF (CF 3 ) CF 2 O] m CF (CF 3 ) CH 2 OH
(n + m = 12)
DTFAC: C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) OH
Table 1
Fluorine-containing alcohol boric acid TEOS yield Yield Particle size
Example abbreviation mg mM (mg) ml mM (mg) (%) (nm)
1 OXF3PO 1250 2.23 60 − − 1061 81 313.0 ± 46.0
2 OXF3PO 1250 2.23 30 − − 1152 90 288.0 ± 78.0
3 OXF3PO 5600 10.0 30 0.05 0.23 1011 79 266.0 ± 30.0
4 OXF3PO 1250 2.23 60 0.10 0.45 1166 89 65.7 ± 8.9
5 OXF14PO 1000 0.42 6.5 − − 393 39 128.0 ± 14.0
6 OXF14PO 1000 0.42 13 − − 365 36 262.0 ± 59.0
7 OXF14PO 1000 0.42 26 − − 349 34 15.7 ± 1.0
8 DTFAC 100 0.19 12 − − 108 96 105.0 ± 25.0
9 DTFAC 100 0.19 5.9 − − 103 97 10.8 ± 1.1
10 DTFAC 100 0.19 2.9 − − 99 96 313.0 ± 78.0
Table 2
Water (Elapsed time: minutes)
Example n-Dodecane 0 5 10 15 20 25 30
Example 1 49 62 56 50 45 36 30 29
〃 2 20 67 65 62 60 59 56 56
3 3 47 44 42 41 37 36 33 31
4 4 40 25 21 19 17 16 15 14
5 5 53 53 50 49 47 46 45 42
6 6 53 55 56 53 50 48 47 44
7 7 56 58 49 48 47 44 43 42
8 8 38 77 74 69 63 57 57 60
9 9 49 71 69 66 60 53 47 43
〃 10 50 100 93 93 86 80 80 80
比較例1
コーティングされていないガラス基材について、実施例1と同様に液滴の接触角測定が行われた。
Comparative Example 1
For the uncoated glass substrate, the contact angle of the droplet was measured in the same manner as in Example 1.
比較例2
ホウ酸を用いてコーティングされたガラス基材について、実施例1と同様に液滴の接触角測定が行われた。
Comparative Example 2
For the glass substrate coated with boric acid, the contact angle of the droplet was measured in the same manner as in Example 1.
比較例3〜5、参考例1〜2
実施例1の液滴の接触角測定において、含フッ素ホウ酸コンポジット粒子メタノール分散液の代わりに下記試料のメタノール分散液(5g/L)を用いてコーティングされたガラス基材が用いられた。
比較例3:ホウ酸/TEOS
比較例4:CF 3 (CF 2 ) 5 (CH 2 ) 2 OH〔FA-6〕
比較例5:FA-6/TEOS
参考例1:OXF3PO
参考例2:OXF14PO
ただし、比較例3では、実施例1においてOXF3POが用いられず、ホウ酸50mg(0.81ミリモル)、TEOS 0.10ml(0.45ミリモル)が用いられ、生成物の収量は130mg、収率は90%であった。また、比較例5では、実施例1においてホウ酸が用いられず、OXF3POの代わりにFA-6 1100mg(3.02ミリモル)が、さらにTEOS 0.10ml(0.45ミリモル)が用いられ、生成物の収量は763mg、収率は68%であった。
Comparative Examples 3-5 , Reference Examples 1-2
In the measurement of the contact angle of the droplets of Example 1, a glass substrate coated with the following sample methanol dispersion (5 g / L) was used instead of the fluorine-containing boric acid composite particle methanol dispersion.
Comparative Example 3: Boric acid / TEOS
Comparative Example 4: CF 3 (CF 2 ) 5 (CH 2 ) 2 OH [ FA-6 ]
Comparative Example 5: FA-6 / TEOS
Reference example 1 : OXF3PO
Reference example 2 : OXF14PO
However, in Comparative Example 3, OXF3PO was not used in Example 1, but boric acid 50 mg (0.81 mmol) and TEOS 0.10 ml (0.45 mmol) were used. The yield of the product was 130 mg and the yield was 90%. It was. In Comparative Example 5, boric acid is not employed in Example 1, FA-6 1100 mg instead of OXF3PO (3.02 mmol) further TEOS 0.10 ml (0.45 mmol) is used, the yield of the product 763mg The yield was 68%.
以上の各比較例および参考例で得られた結果は、次の表3に示される。
表3
水 (経過時間:分)
例 n-ドデカン 0 5 10 15 20 25 30
比較例1 0 50 − − − − − −
〃 2 22 66 − − − − − −
〃 3 20 55 − − − − − −
〃 4 30 43 39 35 31 22 21 16
〃 5 11 36 32 28 21 17 13 7
参考例1 45 62 60 58 56 55 50 53
〃 2 58 63 54 51 49 47 45 42
The results obtained in the above comparative examples and reference examples are shown in the following Table 3.
Table 3
Water (Elapsed time: minutes)
Example n-Dodecane 0 5 10 15 20 25 30
Comparative Example 1 0 50 − − − − − −
〃 2 22 66 − − − − − −
3 3 20 55 − − − − − −
4 4 30 43 39 35 31 22 21 16
11 5 11 36 32 28 21 17 13 7
Reference Example 1 45 62 60 58 56 55 50 53
〃 2 58 63 54 51 49 47 45 42
Claims (12)
RF-A-OH 〔I〕
(ここで、RFは炭素数6以下のパーフルオロアルキル基であり、またはパーフルオロアルキル基のフッ素原子の一部が水素原子で置換され、炭素数6以下の末端パーフルオロアルキル基および炭素数6以下のパーフルオロアルキレン基を含んで構成されるポリフルオロアルキル基であり、Aは炭素数1〜6のアルキレン基である)で表される含フッ素アルコールまたは含フッ素アルコールとこれに対してモル比1.0以下のアルコキシシランとの両者およびホウ酸の縮合体からなる含フッ素ホウ酸コンポジット粒子。General formula
R F -A-OH (I)
(Wherein R F is a perfluoroalkyl group having 6 or less carbon atoms, or a part of the fluorine atom of the perfluoroalkyl group is substituted with a hydrogen atom, and the terminal perfluoroalkyl group having 6 or less carbon atoms and the carbon number 6 or less perfluoroalkylene group, and A is an alkylene group having 1 to 6 carbon atoms). Fluorine-containing boric acid composite particles comprising both an alkoxysilane having a ratio of 1.0 or less and a condensate of boric acid.
CnF2n+1(CH2)jOH 〔II〕
(ここで、nは1〜6、jは1〜6の整数である)で表されるポリフルオロアルキルアルコールが用いられた請求項1記載の含フッ素ホウ酸コンポジット粒子。As the fluorine-containing alcohol represented by the general formula [I], the general formula
C n F 2n + 1 (CH 2 ) j OH (II)
The fluorine-containing boric acid composite particle according to claim 1, wherein a polyfluoroalkyl alcohol represented by the formula (where n is an integer of 1 to 6 and j is an integer of 1 to 6) is used.
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOH 〔III〕
(ここで、nは1〜6、aは1〜4、bは0〜2、cは1〜3の整数である)で表されるポリフルオロアルキルアルコールが用いられた請求項1記載の含フッ素ホウ酸コンポジット粒子。As the fluorine-containing alcohol represented by the general formula [I], the general formula
C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c OH (III)
The polyfluoroalkyl alcohol represented by (wherein n is 1 to 6, a is 1 to 4, b is 0 to 2, and c is an integer of 1 to 3) is used. Fluoroboric acid composite particles.
(R1O)pSi(OR2)q(R3)r 〔IV〕
(ここで、R1、R3はそれぞれ水素原子、炭素数1〜6のアルキル基またはアリール基であり、R2は炭素数1〜6のアルキル基またはアリール基であり、ただしR1、R2、R3は共にアリール基であることはなく、p+q+rは4であり、ただしqは0ではない)で表わされるシラン誘導体である請求項1記載の含フッ素ホウ酸コンポジット粒子。Alkoxysilane has the general formula
(R 1 O) p Si (OR 2 ) q (R 3 ) r (IV)
(Where R 1 and R 3 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group, and R 2 is an alkyl group having 1 to 6 carbon atoms or an aryl group, provided that R 1 , R 3 2. The fluorine-containing boric acid composite particle according to claim 1, wherein both R 2 and R 3 are not aryl groups, and p + q + r is 4 (where q is not 0).
RF′-A-OH 〔Ia〕
または一般式
HO-A-RF′′-A-OH 〔Ib〕
(ここで、RF′は炭素数6以下の末端パーフルオロアルキル基および炭素数6以下のパーフルオロアルキレン基を有する、O、SまたはN原子を含有する直鎖状または分岐状パーフルオロアルキル基であり、RF′′は炭素数6以下のパーフルオロアルキレン基を有する、O、SまたはN原子を含有する直鎖状または分岐状のパーフルオロアルキレン基であり、Aは炭素数1〜6のアルキレン基である)で表される含フッ素アルコールまたは含フッ素アルコールとこれに対してモル比1.0以下のアルコキシシランとの両者およびホウ酸の縮合体からなる含フッ素ホウ酸コンポジット粒子。General formula
R F ′ -A-OH (Ia)
Or general formula
HO-AR F ′ ′ -A-OH (Ib)
(Wherein R F ′ is a linear or branched perfluoroalkyl group containing an O, S or N atom having a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms. R F ″ is a linear or branched perfluoroalkylene group containing an O, S or N atom having a perfluoroalkylene group having 6 or less carbon atoms, and A is 1 to 6 carbon atoms. Fluorine-containing boric acid composite particles comprising a condensate of boric acid and both a fluorine-containing alcohol represented by the following formula:
CmF2m+1O〔CF(CF3)CF2O〕dCF(CF3)(CH2)eOH 〔IIa〕
(ここで、mは1〜3、dは0〜100、eは1〜3の整数である)で表されるヘキサフルオロプロペンオキシドオリゴマーアルコールが用いられた請求項6記載の含フッ素ホウ酸コンポジット粒子。As the fluorine-containing alcohol represented by the general formula [Ia], the general formula
C m F 2m + 1 O (CF (CF 3 ) CF 2 O] d CF (CF 3 ) (CH 2 ) e OH (IIa)
The fluorine-containing boric acid composite according to claim 6, wherein a hexafluoropropene oxide oligomer alcohol represented by the formula (wherein m is 1 to 3, d is 0 to 100, and e is an integer of 1 to 3) is used. particle.
HO(CH2)fCF(CF3)〔OCF2CF(CF3)〕gO(CF2)hO〔CF(CF3)CF2O〕i
CF(CF3)(CH2)fOH 〔IIb〕
(ここで、fは1〜3、g+iは0〜50、hは1〜6の整数である)で表されるパーフルオロアルキレンエーテルジオールが用いられた請求項6記載の含フッ素ホウ酸コンポジット粒子。As the fluorine-containing alcohol represented by the general formula [Ib], the general formula
HO (CH 2 ) f CF (CF 3 ) [OCF 2 CF (CF 3 )] g O (CF 2 ) h O [CF (CF 3 ) CF 2 O] i
CF (CF 3 ) (CH 2 ) f OH (IIb)
The fluorine-containing boric acid according to claim 6, wherein a perfluoroalkylene ether diol represented by the formula (wherein f is 1 to 3, g + i is 0 to 50, and h is an integer of 1 to 6) is used. Composite particles.
(R1O)pSi(OR2)q(R3)r 〔IV〕
(ここで、R1、R3はそれぞれ水素原子、炭素数1〜6のアルキル基またはアリール基であり、R2は炭素数1〜6のアルキル基またはアリール基であり、ただしR1、R2、R3は共にアリール基であることはなく、p+q+rは4であり、ただしqは0ではない)で表わされるシラン誘導体である請求項6記載の含フッ素ホウ酸コンポジット粒子。Alkoxysilane has the general formula
(R 1 O) p Si (OR 2 ) q (R 3 ) r (IV)
(Where R 1 and R 3 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group, and R 2 is an alkyl group having 1 to 6 carbon atoms or an aryl group, provided that R 1 , R 3 7. The fluorine-containing boric acid composite particle according to claim 6, wherein both R 2 and R 3 are not aryl groups, and p + q + r is 4 (where q is not 0).
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10104403A (en) * | 1996-10-02 | 1998-04-24 | Nippon Kayaku Co Ltd | Sheet having stainproof property and hard coating property |
JP2003138213A (en) * | 2001-11-07 | 2003-05-14 | Sony Corp | Composition for surface modified film, surface modified film, filter for display and display |
JP2011063708A (en) * | 2009-09-17 | 2011-03-31 | Unimatec Co Ltd | Surface-treating agent |
JP2014501804A (en) * | 2010-11-10 | 2014-01-23 | スリーエム イノベイティブ プロパティズ カンパニー | Surface treatment process, composition used in the process, and treated article |
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US2951871A (en) * | 1959-07-21 | 1960-09-06 | Olin Mathieson | Polyfluoroalkyl borates |
US3574770A (en) | 1968-10-24 | 1971-04-13 | Nasa | Hydroxy terminated perfluoro ethers |
JPH05186719A (en) | 1991-05-31 | 1993-07-27 | Hitachi Chem Co Ltd | Inorganic conductive coating composition and production of conductive coating film therefrom |
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JP3728752B2 (en) | 2003-03-19 | 2005-12-21 | 荒川化学工業株式会社 | Curable composition and cured product thereof |
JP2007186454A (en) | 2006-01-13 | 2007-07-26 | Yunimatekku Kk | Fluorine-containing ether alcohol and method for producing the same |
CA2643067C (en) | 2006-03-10 | 2012-06-19 | Unimatec Co., Ltd. | Polyfluoroalkyl alcohol, or (meth)acrylic acid derivative thereof, and process for producing the same |
JP5292680B2 (en) | 2006-08-07 | 2013-09-18 | ユニマテック株式会社 | Fluorine-containing polyether (meth) acrylate and process for producing the same |
US8946486B2 (en) * | 2007-12-03 | 2015-02-03 | Tyco Fire & Security Gmbh | Method of forming alkoxylated fluoroalcohols |
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